Fixation of sizes



' 'Patented Dec. 23, 1941 i .UNITEDSTATES PATENT 1 o F FlCE 2,267,265 I 'mA'rroN or SIZES Louis.H. Bock and Alva'L. Honk, Philadelphia,

Pa., assignors to Riilnn adelphla, Pa. No Drawing.

Application February 6, 1939, Serial No. 254,884

& Baas Company, Phil- 12 Claims. ((31. 91-10) This invention relates to a new process for converting water-soluble or water-dispersible, high molecular weight compounds containing a multiplicity of hydroxyl groups into complexes which are insoluble in water. It particularly deals with the fixation of polymeric hydroxyl- 7 containing products such as polyvinyl alcohol 1 and the polysaccharides which include amylaceous and cellulosic'sizing or finishing materials.

It more particularly relates to the insolubilizing of water-soluble or water-dispersible sizing, coating, and finishing preparations upon textile fabrics, yarns, fibers and similar materials with condensates of phenols, formaldehyde and nonaromatic secondary amines.

The high molecular weight, hydroxyl-containing substances, which are water-soluble or readily dispersible in water, enjoy the advantage of easy application for impregnating or coating, but they sufier the serious disadvantage that they are readily dispersed again by water. For example, starch, the most common coating or $12-' ing material for. textiles, is not resistant to laundering. For many purposes it would be desirable to provide a starched'finish which-is resistantto' removal in laundering and which is not seriously impaired when moistened. Polyvinyl alcohol and water-soluble cellulose ethers possess-valuble properties for sizing which havenot as yet been utilized in full measure, in part, at least, because they are not water-resistant.

It is an object of this invention "toiprovi e a method of rendering water-soluble orwater-dispersible, hydroxyl-containing sizing materials of high molecular weight relatively insoluble. It is an object to provide a means for improving the fastness of starch, polyvinyl alcohol and cellulosic sizings or coatings. It is a further object to provide a simple but effective one-bath process for the fixation of these sizing materials on textile fibers, yarns, fabrics, straw, paper and simialicyclic acyl groups; Ri-and R: represent menibers'of the group of alicyclic and aliphatic radicals and divalent groups which jointly with the nitrogen form a heterocyclic ring; and a and b are each whole numbers under five.

The "essential characteristic of these compounds is the aromatic methylene-nitrogen linkage, and the presence of at least one group containing a nuclearly-bound oxygen atom on the aromatic group. This oxygen atom may be present in ahydroxylgroup, an ether group carrying a C=C linkage in the Bar-Position, or an ester group. While the exact nature of the other substituents in the aromatic ring is not of direct importance as far as the fixation of water-dispersible, hydroxyl-containing sizes is concerned, the substituent groups do have an influence on the finish of textile materials, as will be discussed below.

lar materials. It is another object to stiffen fabrics permanently. Other objects will become evident from the discussion which follows.

These objects are accomplished by the use of derivatives of phenols which possess the following general structure mohair-(cam wherein Ar represents an aromatic nucleus which may be substituted by one or more members of the group consisting of aliphatic or alicyclic hydrocarbon groups, alkoxy, aryloxy, acyl, acylamido, nitro, halogen, or aryl sulfonyl, etc. radicals; X represents a member of the group consisting of hydrogen, aralkyl and p,'y-unsaturated aliphatic hydrocarbon groups and aliphatic and The compounds are obtained by condensing a methylol-forniing phenol with formaldehyde and 1 mol phenol, 1 mol formaldehyde, and 1 mol dimethyl amine, identified as hydroxybenzy dimethyl amine.

1 mol phenol, 2,mols formaldehyde, and 2 mols dimethyl amine. I

1 mol phenol, 3 mols formaldehyde, and 3 mols dimethyl amine.

1 mol p-ter-butyl phenol, 1 mol formaldehyde,

and 1 mol dimethyl amine. 1 mol p-a,a,7,'y-tetramethyl butyl phenol, 1 mol formaldehyde, and 1 mol dimethyl amine.

1 mol octadecyl phenol, 1 mol formaldehyde, and;

1 mol diethyl amine. 1 mol p-hydroxydiphenyl, 1 mol formaldehyde,

' and 1 mol morpholine.

.1 mol p,p-di-(hydroxy.phenyl) propane, 2 mols formaldehyde, and 2 mols dimethyl amine. 1 mol fl-naphthol, 1 mol formaldehyde, and 1 mol dimethyl amine. 1 mol p-a,a,'y,-y-tetramethylbutyl resorcinol, 1 mol formaldehyde, and 1 mol morpholine. I 1 mol di-hydroxyphenyl 'sulfone, 2 mols formaldehyde and 2 mols dimethyl amine. 1 mol 2-chlo'ro-p-cresol, 1 mol formaldehyde, and

1 mol dimethyl amine.

1 mol p-ter-butyl phenol, 1 mol formaldehyde,

and 1 mol diethanol-amine. 1 mol p-nitrophenol, '1 mol formaldehyde, and 2 mols dimethyl amine. 1 mol chloromethyl phenyl allyl ether and 1 mol dimethyl amine.

l 1 mol chloromethyl phenyl methallyl ether and 1 It should be observed that the phenols which are reacted above belong to the general class of hydroxy or polyhydroxy, aromatic compounds which possess at least one reactive nuclear position which is orth'o or para to a phenolic hydroxyl group. These compounds are conveniently termed methylol-formmg" phenols. They may be of monocyclic or polycyclic structure.

When more than one nuclear position is open for substitution, more than one methylene linkage is possible and multiple equivalents of formaldehyde and amine may be used to substitute one or more positions of the aromatic ring. Some of these poly-substituted phenols are particularly effective in rendering water-dispersible sizes insoluble.

In addition to the free ph'enolic forms which are shown above, and in the patents above-mentioned, there may be used the ethers, esters and the quaternary ammonium derivatives ofthe phenolic condensates with formaldehyde and non-aromatic secondary amines. The esters and quaternary ammonium derivatives that may be used have been described in-application Serial No. 240,009, filed November 12, 1938, and application Serial No. 244,923, filed December 10,

These include such esters as:

Laurie acid ester of hydroxybenzyl dimethyl O II (onoFcnwHiwHm-O oooni The ethers which are effective in the fixation of sizes are those which carry a double bond in the {S n-position in the group designated as X in the general formula given above. Typical unsaturated groups include allyl, methallyl, crotyl, and benzyl. The ethers are useful in their amine form, in their acid salt form or in -their 1118M.-

The water-soluble r water-dispersible polyhydroxy.

5 which' are useful for sizing or finishing include cellulose ethers, such as the water-soluble forms of methyl and ethyl cellulose, hydroxyethyl cellulose and the like, polyvinyl alcohol, and the starches, including corn, rice, tapioca, sago,

1o wheat, potato, etc., starches proper, flours containing starches, modified starches, oxidized starches, converted starches, etc. Other finishing agents may be added, such as fillers, pigments, softeners, resins, etc.

react with polyhydroxy sizing compounds at elevated temperatures with or without the presence of alkaline or acidic catalysts to form insolu-' ble stable derivatives or complexes. In carrying 20 out the process, preferably 2 parts of a compound of the above general type is added to a solution containing from about 1 to about parts of a water-dispersible, polyhydroxy sizing material, such as starch, hydroxyethyl cellulose or polyvinyl alcohol. The phenolic derivative may be added to the dispersion or solution of the size in the form of a soluble salt or it may be suspended in the form of the, free base. This sizing preparation is used to impregnate or coat with the compound used and with the time of application. In general, a temperature of 120.- 140 C. for or more minutes will suffice. A higher temperature up to 160 C. may be used w for a shorter period. In plant practice the heating may be accomplished while the cloth is passing over heated rollers or through a hot oveni such as a loop dryer, closed tenter, or the like. An advantage of these fixation agents is that they permit the use of a one-bath sizing operation. Yet these compounds may also be applied to fibers, fabric or yarn prior to the sizing op-' eration proper or they may be applied in a bath which follows the step of impregnating or coating with a sizing. agent. Mixtures containing both and fixing agent may be prepared ready for use. After any impregnating or treating process, it is necessary to use heat to fix the size. The sized material may then be washed, if desired, to remove by-products, unreacted substances, etc. v Further details of the process of treating water-dispersible, hydroxyl-containing sizing materials will be evident from consideration of the following examples. Example 1 Cotton lawn was run on a quetch with the box holding an aqueous solution containing 6.6% hydroxyethyl cellulose and 2.3% of the acetic acid salt of the product obtained by condensing 1 mol of phenol, 2 mols of formaldehyde and 2- mols of dimethyl amine. From the padder-the material was passed through a tenter with air heated to approximately 300 F. at such a speed as to allow sufilcientti'me for drying and subsequent reaction of the hydroxyethyl cellulose. and the phenolic compound. From the tenter the fabric passed through a three roll hot calender.

The resulting finish was smooth, lustrous, and

high molecular weight, compounds The compounds of the type illustrated above Then the fabric, with or without prefirm. After a thorough washing in soap tion, the finish was still firm.

Example 2 A 68 x 72, 4 yard cotton sheeting was impregnated with an aqueous mixture comprised of parts of a 7.3% solution of hydroxyetliyl cellusoluprior to the nip.

lose and 1 part of a solution of the acetic I acid salt of the product obtained by condensing 1 mol of phenol, 3 mols of formaldehyde and 3 mols of dimethyl amine. The fabric was passed through a tenter at 260 F. at such a speed as to bring about drying and fixation of the starch. It was then washed and ironed. A good permament stiffening resulted.

Example 3 Viscose rayon fabric was padded with good pressure with an aqueous paste containing 7.3%

tapioca starch and 3.5% of the acetic acid salt' of the'product obtained by condensing 1 mol of cloth was dried in aloop drier at 170 F. at such a speed that the cloth was just dry (8-10% mois ture) on emerging from the drier. The fabric was then passed through a heated frictioncalender at lbs. steam pressure, the fabric being slightly moistened by a fine water spray ius't The finished fabric was full,

.firm, leathery and with. an exceptionally high degree of gloss. On laundering the cloth retains its fullness and firmness and a considerable degree of its gloss.

Example 8 I g A 60s, 2 ply, 3 cable cotton cord was impreg- I nated with a mixture of 10 parts of 8% potato starchsolution and 2.5 parts of the acetic acid salt of the product obtained bycondensing 1 mol 'of 2-chloro-4-methyl phenol, 1 mol of formaldehyde and 1 mol of dimethyl amine. It was dried,

phenol with 2 mols of formaldehyde and 2 mols' of dimethyl amine. The fabric was passed through a tenter at 260 F. at such a speed as to bring about drying and fixation of the starch.

, It possessed a stiff, smooth finish, not removed by washing.

Example 4 d A 64; 64, 5 yard cotton sheeting was backfilled with a mixture comprising 7.5% potato starch,

5% tale, 5% sulfonated tallow, and 2% of the aceticacid salt of the product obtained by condensing 1 mol of .p-a,a,-y,'y-tetramethyl butyl phenol, 1 mol of formaldehyde, and 1 mol of (ii,-

methyl amine. The sheeting was dried'and heated at 275-280 F. in a tenter. It was then passed over a single nip, two roll, cold calender. A moderate stifiening resulted, persisting through laundering operations. The finish obtained was full and moderately firm. The filler was well bound.

Example 5' An aqueous mixture containing 6.65% hydroxyethyl cellulose and 2.3% of the aceti'c acid salt of the product obtained by condensing 1 mol of di-p-hydroxyphenyl sulfone with 2 mols of formheated at 275 and polished with. high speed friction rollers. The resulting cord was quite stiff and the stiffness was permanent to washing,

Example 9 Cotton sheeting was impregnated with a mixture comprising 9% polyvinyl alcohol, a trace of sodium carbonate and 2.5% of the oleic acid ester of hydroxybenzyl dimethyl benzyl ammoni'-.

- sisting of 100 parts of an aqueous solution containing 7 hydroxyethyl cellulose and 0.25%

. sodium carbonate, and 5 parts of the acetic ester aldehyde and 2 mols of dimethyl amine waspadded on cotton cloth, dried and baked at 280-300 F. After a thorough washing the cloth retained a very stifi finish, resistant to further washing.

Example 6 An 80 x 80, 4 yard cotton print cloth was treated to give localized pattern efiects by screen printing, using a paste comprising 2.5% watersoluble ethyl cellulose, 1.5% of the product obtained by condensing 1 mol of oleyl phenol, 1 mol of formaldehyde, and 1 mol of dimethyl amine, and 2% of an ultramarine blue pigment. fabric was then dried on a bank of eight cans at 15 1b. steam pressure and passed through a loop drier heated to 280 F. to cause reaction of the ethyl cellulose and the phenolic derivative.

. From the drier the cloth was calendered. The

design produced was flexible and resistant to dry cracking and bleeding off when washed.

Example 7 of ter-butyl hydroxybenzyl dimethyl benzyl ammoniumchloride. This compound was obtained by the condensation of equimolecular, quantities of ter-butyl phenol, formaldehyde and dimethyl amine, followed by esterification with acetyl chlo-' ride. The free base was then converted to the quaternary salt with benzyl chloride. The coated cloth was squeezed and dried and then treated 20 minutes at 130 C. A very stiff, papery finish was obtained, which was only slightly softened by washing. Y

Example 11 Cotton fabric was coated with a paste comprising 20 parts of an 8% solution of potato starch, a trace. of sodium carbonate, and 1 part of the productobtained by reacting p,p-di(hydroxyphenyl) propane with 2 mols each of formaldehyde and dimethylamine, followed by esterification with acetyl chloride, after which the free base was converted to the quaternary ammonium salt with benzyl chloride. The cloth was squeezed and baked at C. for 30 minutes. A very stiff permanent finish resulted.

Example 2 I I Cotton sheeting was-coated with a mixture consisting of 5 parts of an 8% paste of potato starch and one part of a 25% solution of the acetic acid 'salt of the condensation product obtained from one mol of guaiacol, one mol of formaldehyde,

and one mol of dimethyl amine. The coated cloth was dried and baked at 130 C. for 30 minutes. A very stiff, washfast finish was obtained.

Example 13 Cotton sheeting was coated with a mixture consisting of 10 parts of an 8% solution of potato starch and 1 part of a25% solution of the acetic The cloth "was A- very stifiwashfast finish was obtained. a

While the compounds described herein are generally applicable for the processes outlined, it

has been found that they behave somewhat differently depending on their molecular weight. The products obtained from phenols containing long chain substituents give soft, smooth finishes.

It is. obvious that the s'tiffnessof a finish can.

also be varied by the type of starch used, the viscosity of the cellulose ether, etc.- Further,

when long chained products are used to fix size, the fabric does not readily absorb water and a certain degree of water-repellency is secured.

The process ofinsolubilizing sizes or impr'ov ing the fastness of 'water-dispersible sizes herein disclosed may be applied to yarn, fabric, thread or fibers of any material which may be heated over 120 C. without seriously damaging the sized material. The process is thus applicable to such materials as cotton, linen, paper, straw, jute, hemp, and thevarious synthetic cellulosic fibers. We claim: 3 1. A process for improving the fastness of starch sizing upon textile material, which comprises impregnating said material with a starch anda phenolic derivativeand subsequently heating the impregnated material; said phenolic derivative being selected from the group consisting of (l) phenolic methylene tertiary amines in which .two of the N-substituents are chosen from the group consisting of aliphatic and alicyclic radicalsand divalent groups which jointly formwith the nitrogen a heterocyclic ring, 'and in which the oxygen atom'of the phenolic group 3 bears a substituent selected from the group consisting of hydrogen, aralkyl and S -unsaturated aliphatic hydrocarbon groups, and aliphatic and alicyclic acyl radicals, (2) the acid salts of said amines and (3) the quaternary salts of said amines.

2. A process for improving the fastness of polyvinyl alcohol sizing upon textile material, which comprises impregnating said material with a polyvinyl alcohol and a phenolic derivative and subsequently heating the impregnated material; said phenolic derivative being selected from the group consisting of (l) phenolic methylene tertiary amines in which two of the N-substituents are jointly form with the nitrogen a heterocyclic ring, and in which the oxygen atom of the phenolic group bears a substituent selected from the group.

consisting of hydrogen, aralkyl and fin-unsaturated aliphatic hydrocarbon groups, and aliphatic and alicyclic acyl radicals, (2) the acid salts of said amines and (3) the quaternary salts of said amines.

' 3. A process for improving the fastness of water-soluble cellulose ether sizing upon textile material, which comprises impregnating said material with a water-soluble cellulose ether and a phenolic derivative and subsequently heating the impregnated material; said phenolic derivative being selected from the group consisting of (1) phenolic methylene tertiary amines inwhich two of the N-substituents are chosen from the group consisting of aliphatic and alicyclic radicals and divalent groups which jointly form with the mtrogen a heterocyclic ring, and in which the oxyacid'salt 'of the condensation product obtained 1 from 1 mo] of chloromethyl phenyl benzyl ether and 1 mol of dimethyl amine. I then dried and baked at 130C. for 30 minutes.

gen atom of the phenolic group bears a substituent selected from the group consisting of hydro,-,

gen aralkyl and pig-unsaturated aliphatic hydrocarbon groups, and aliphatic and alicyclic acyl radicals, (2) the acid salts of said amines and --(3) the quaternary salts of said amines.

'4. A process for improving the fastness of ,wa-

ter-dispersible, hydroxyl-containing size upon textile material, which comprises impregnating said material with said size and 'a phenolic derivative and subsequently. heating the treated -material;' said phenolic derivative being selected from the group consisting of 1) phenolic methylene tertiary amines in which two of the N-sub-' stituents are chosen from the group consisting of aliphatic and alicyclic radicals and divalent groups which *jointly form with the nitrogen a heterocyclic ring, and in which'the oxygen atom of the. phenolic group bears a'substituent selected from the group eon'sisting'of hydrogen, aralkyl and 3,7 lunsaturated aliphatic hydrocarbon,

groups, and aliphatic and alicyclic acyl radicals,

(2) the acid salts of said amines and (3) 'the' quaternary salts of said amines.

5. A process for insolubilizing a water-soluble 'cellulose ether size, which comprises, treating textile material with said size and with a nitrogenous condensate of a methylol-forming phenol,

formaldehyde, and a strongly basic, non-aromatic secondary amine and subsequently heating said I treated material.

starch size, which comprises treating textile ma- 6. A-process for improving thefastness of terial'with said size and with a nitrogenous conchosen from the group consisting of aliphatic and alicyclic radicals and divalentgroups which water-dispersible,

densate of a methylol-forming phenol, formalde- ,hyde,an'd a'strongly basic, non-aromatic secondary amine and subsequently heating said treated material.

7. .A process for increasing the fastness of size containing polyvinyl alcohol which comprises treating textile material with said size and with a nitrogenous condensateof a methylol-forming phenol, formaldehyde, and a strongly basic, nonaromatic secondary amine and subsequently heating said treated material.

' consisting of aliphatic and alicyclic radicals and divalent groups which Jointly form with the nitrogen a heterocyclic ring, and in which the oxygen atom of the phenolic group bears a substituent selected-from the group consisting of hydrogen, aralkyl and Fry-unsaturated aliphatic hydrocarbon groups, and aliphatic and alicyclic acyl radicals, (2) the acid salts of said'amines and 3) the quaternary salts of said amines.

l0. Textile material carrying as a size a complex reaction product of a starch and a phenolic derivative selected from the group consisting of (.1) phenolic methylene tertiary amines in which J two of the N-substituents are chosen from the group consisting of aliphatic and alicyclic radicals and divalent groups which jointly form with the nitrogen a heterocyclic ring, and in which the oxygen atom of the phenolic group bears a sub-. stituent selected from the group consisting of hydrogen, aralkyl and pry-unsaturated aliphatic hydrocarbon groups, and aliphatic and alicyclic acyl radiacals, (2) the acid salts of said amines and (3) the quaternary salts of said amines.

11. Textile material carrying as a size a complex reaction product of a polyvinyl alcohol and a phenolic derivative selected from the group consisting of (1) phenolic methylene tertiary amines in which two of the N-substituents are chosen from the group consisting of aliphatic and alicyclic radicals and divalent groups which jointly form with the nitrogen a heterocyclic ring, and in which the oxygen atom of the phe-- nolic group bears a substituent selected from the group consisting of'hydrog'en, aralkyl and 5, unsaturated aliphatic hydrocarbon groups, and aliphatic and alicyclic acyl radicals, (2) the acid salts of said amines and (3) the quaternary salts of said amines.

12. Textile material carrying as a size a complex reaction productof a cellulose ether and a phenolic derivative selected from the group consisting of (1) phenolic methylene tertiary amines in which two of the N-substituents are chosen from the group consisting of aliphatic and alicyclic radicals and divalent groups which jointly form with the nitrogen a heterocyclic ring, and in which the oxygen atom of the phenolic group bears a substituent selected from the group consisting'of hydrogen, aralkyl and 8, unsaturated aliphatic hydrocarbon groups, and aliphatic and alicyclic acyl radicals, (2) the acid salts of said amines and (3) the quaternary salts of said amines.

LOUIS H. BOCK.

ALVA L. HOUK. 

